Formulations and method for post-CMP cleaning

Abstract

The present invention is a method of cleaning to removal residue in semiconductor manufacturing processing, comprising contacting a surface to be cleaned with an aqueous formulation having a polymer selected from the group consisting of acrylamido-methyl-propane sulfonate) polymers, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer and mixtures thereof and a quaternary ammonium hydroxide having greater than 4 carbon atoms or choline hydroxide with a non-acetylinic surfactant. The present invention is also a post-CMP cleaning formulation having the components set forth in the method above.

The invention claimed is: 
     
       1. A method of cleaning to remove residue in semiconductor manufacturing processing, comprising:
 contacting a surface to be cleaned with an aqueous formulation having a polymer selected from the group consisting of acrylamido-methyl-propane sulfonate) polymers, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer and mixtures thereof, and a quaternary ammonium hydroxide selected from the group consisting of: quaternary alkyl ammonium hydroxide having greater than 4 carbon atoms and choline hydroxide. 
 
     
     
       2. The method of  claim 1  wherein the semiconductor manufacturing processing is selected from the group consisting of post-CMP cleaning, photo-resist ash residue removal, photoresist removal, back-end packaging, pre-probe wafer cleaning, dicing, and grinding and photo-voltaic substrate cleaning. 
     
     
       3. The method of  claim 1  wherein the surface comprises copper patterns on a dielectric substrate. 
     
     
       4. The method of  claim 1  wherein the polymer is present in a concentration of 1 ppb to 10 wt &. 
     
     
       5. The method of  claim 1  wherein the polymer is present in a concentration of 0.1 ppm to 5 wt %. 
     
     
       6. The method of  claim 1 , wherein the formulation further comprises an organic acid. 
     
     
       7. The method of  claim 6  wherein the organic acid is selected from the group consisting of oxalic acid, citric acid, maliec acid, malic acid, malonic acid, gluconic acid, glutaric acid, ascorbic acid, formic acid, acetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, glycine, alanine, cystine, salts of such acids and mixtures thereof. 
     
     
       8. The method of  claim 1  wherein the quaternary alkyl ammonium hydroxide having greater than 4 carbon atoms has less than sixteen carbon atoms. 
     
     
       9. The method of  claim 1 , wherein the formulation further comprises a surfactant, wherein the surfactant is selected from the group consisting of acetylinic diol surfactants, silicone surfactants, poly(alkylene oxide) surfactants, fluorochemical surfactants, octyl and nonyl phenol ethoxylates, alcohol ethoxylates, (C 16 H 33 (OCH 2 CH 2 ) 10 OH) (ICI), (C 16 H 33 (OCH 2 CH 2 ) 20 OH), amine ethoxylates, glucosides, glucamides, polyethylene glycols, poly(ethylene glycol-co-propylene glycol), linear alkylbenzenesulfonates (LAS), secondary alylbenzenesulfonate, fatty alcohol sulfates (FAS), secondary alkanesulfonates (SAS) and in some cases also fatty alcohol ether sulfates (FAES) and mixtures thereof. 
     
     
       10. The method of  claim 1 , wherein the formulation further comprises a chelating agent. 
     
     
       11. The method of  claim 10  wherein the chelating agent is selected from the group consisting of ethylenediaminetetracetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid (NHEDTA), nitrilotriacetic acid (NTA), diethylklenetriaminepentacetic acid (DPTA), ethanoldiglycinate, citric acid, gluconic acid, oxalic acid, phosphoric acid, tartaric acid, methyldiphosphonic acid, aminotrismethylenephosphonic acid, ethylidene-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, ethylaminobismethylenephosphonic acid, dodecylaminobismethylenephosphonic acid, nitrilotrismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, hexadiaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and 1,2-propanediaminetetetamethylenephosphonic acid, maronic acid, succinic acid, dimercapto succinic acid, glutaric acid, maleic acid, phthalic acid, fumaric acid, polycarboxylic acids, tricarbaryl acid, propane-1,1,2,3-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, pyromellitic acid, oxycarboxylic acids, glycolic acid, β-hydroxypropionic acid, citric acid, malic acid, tartaric acid, pyruvic acid, diglycol acid, salicylic acid, gallic acid, polyphenols, catechol, pyrogallol, phosphoric acids, pyrophosphoric acid, polyphosphoric acid, heterocyclic compounds, 8-oxyquinoline, diketones, α-dipyridyl acetylacetone, salts of the same and mixtures thereof. 
     
     
       12. The method of  claim 1  wherein the quaternary alkyl ammonium hydroxide is selected from the group consisting of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, trimethylethylammonium hydroxide and mixtures thereof. 
     
     
       13. The method of  claim 1 , wherein the formulation further comprises an agent selected from the group consisting of dispersing agents, organic solvents, defoaming agents and mixtures thereof. 
     
     
       14. An aqueous cleaning formulation comprising:
 (a) a polymer selected from the group consisting of acrylamido-methyl-propane sulfonate) polymers, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer, and mixtures thereof; and 
 (b) a quaternary ammonium hydroxide selected from the group consisting of: quaternary alkyl ammonium hydroxide having greater than 4 carbon atoms, and choline hydroxide in the absence of a non-acetylinic surfactant. 
 
     
     
       15. The formulation of  claim 14  wherein the polymer is present in a concentration of 1 ppb to 10 wt %. 
     
     
       16. The formulation of  claim 14  wherein the polymer is present in a concentration of 0.1 ppm to 1000 ppm. 
     
     
       17. The formulation of  claim 14  including an organic acid. 
     
     
       18. The formulation of  claim 17  wherein the organic acid is selected from the group consisting of oxalic acid, citric acid, maleic acid, malic acid, malonic acid, gluconic acid, glutaric acid, ascorbic acid, formic acid, acetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, glycine, alanine, cystine, salts of such acids, and mixtures thereof. 
     
     
       19. The formulation of  claim 14  wherein the quaternary ammonium hydroxide with greater than 5 carbon atoms in their molecular structure has less than sixteen carbon atoms in their molecular structure. 
     
     
       20. The formulation of  claim 14  including a surfactant wherein the surfactant is selected from the group consisting of acetylinic diol surfactants, silicone surfactants, poly(alkylene oxide) surfactants, fluorochemical surfactants, octyl and nonyl phenol ethoxylates, alcohol ethoxylates, (C 16 H 33 (OCH 2 CH 2 ) 10 OH) (ICI), (C 16 H 33 (OCH 2 CH 2 ) 20 OH), amine ethoxylates, glucosides, glucamides, polyethylene glycols, poly(ethylene glycol-co-propylene glycol), linear alkylbenzenesulfonates (LAS), secondary alylbenzenesulfonate, fatty alcohol sulfates (FAS), secondary alkanesulfonates (SAS), fatty alcohol ether sulfates (FAES) and mixtures thereof. 
     
     
       21. The formulation of  claim 14  including a chelating agent. 
     
     
       22. The formulation of  claim 21  wherein the chelating agent is selected from the group consisting of ethylenediaminetetracetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid (NHEDTA), nitrilotriacetic acid (NTA), diethylklenetriaminepentacetic acid (DPTA), ethanoldiglycinate, citric acid, gluconic acid, oxalic acid, phosphoric acid, tartaric acid, methyldiphosphonic acid, aminotrismethylenephosphonic acid, ethylidene-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, ethylaminobismethylenephosphonic acid, dodecylaminobismethylenephosphonic acid, nitrilotrismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, hexadiaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and 1,2-propanediaminetetetamethylenephosphonic acid, maronic acid, succinic acid, dimercapto succinic acid, glutaric acid, maleic acid, phthalic acid, fumaric acid, polycarboxylic acids, tricarbaryl acid, propane-1,1,2,3-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, pyromellitic acid, oxycarboxylic acids, glycolic acid, β-hydroxypropionic acid, citric acid, malic acid, tartaric acid, pyruvic acid, diglycol acid, salicylic acid, gallic acid, polyphenols, catechol, pyrogallol, phosphoric acids, pyrophosphoric acid, polyphosphoric acid, heterocyclic compounds, 8-oxyquinoline, diketones, α-dipyridyl acetylacetone, salts of the same and mixtures thereof. 
     
     
       23. The formulation of  claim 14  wherein the quaternary alkyl ammonium hydroxide is selected from the group consisting of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, trimethylethylammonium hydroxide and mixtures thereof. 
     
     
       24. A post-CMP cleaning formulation comprising;
 (a) Oxalic acid; 
 (b) Secondary alkane sulphonic acid; 
 (c) Acetylinic-based surfactant; 
 (d) quaternary alkyl ammonium hydroxide having greater than 4 carbon atoms; 
 (e) a polymer selected from the group consisting of acrylamido-methyl-propane sulfonate) polymers, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer and mixtures thereof; and, 
 (f) water. 
 
     
     
       25. The formulation of  claim 23 , comprising: 1-6 wt % oxalic acid, 0.1-2 wt % secondary alkane sulphonate, 0.05-1.5 wt % acetylinic-based surfactant, 0.1-3 wt % acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer; quaternary alkyl ammonium hydroxide having greater than 4 carbon atoms to adjust the pH in the range of 1-7, remainder water. 
     
     
       26. The formulation of  claim 24  diluted with water in the range of 1:0 to 1:10000 at the point of use. 
     
     
       27. A post-CMP cleaning formulation comprising;
 (a) ethylene diamine tetraacetic acid; 
 (b) secondary alkane sulphonic acid surfactant; 
 (c) a non-acetylinic-based surfactant; 
 (d) choline hydroxide; 
 (e) a polymer selected from the group consisting of acrylamido-methyl-propane sulfonate) polymers, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer and mixtures thereof; and 
 (f) water.